Thermoset polyimides for microelectronic applications

ABSTRACT

Dendrimer/hyperbranched materials are combined with polyimide to form a low CTE material for use as a dielectric substrate layer or an underfill. In the alternative, ruthenium carbene complexes are used to catalyze ROMP cross-linking reactions in polyimides to produce a class of cross-linkable, thermal and mechanical stable material for use as a dielectric substrate or underfill. In another alternative, dendrimers/hyperbranched materials are synthesized by different methods to produce low viscosity, high Tg, fast curing, mechanically and chemically stable materials for imprinting applications.

BACKGROUND

1). Field

Embodiments relate generally to a method of making materials fordielectric substrate layers and underfills, and more specifically in thesubstrate imprinting process.

2). Discussion of Related Art

Substrate imprinting technology is a process for packaging substratefabrication. A substrate includes non-conductive material which acircuitry pattern is printed. A circuitry pattern is directly printedinto the dielectric layer by imprinting a build-up layer. The currentstate of the art for substrate manufacture utilizes a thermosettingepoxy dielectric film upon which a layer of copper is plated. Thecircuitry is obtained by use of a sacrificial photo-definable layer,which after being developed serves as the mask for etching the exposedcopper and dielectric material. The photo-definable layer is thenremoved and the dielectric layer is cured to form a rigid pattern.

In the current state of the art, chips are electrically connected“face-down” with its electronic components in direct contact with theconductive bumps on the chip-bond pads on the substrates or circuitboards. Using the entire area of the die, this direct connection betweenchip and substrate provides a flexible and mechanically ruggedinterconnection method. An underfill is a dielectric adhesive materialto enhance the performance of a chip by interposing between a chip and asubstrate. An underfill layer serves several purposes. The underfillprovides mechanical strength to the assembly and protects the bumps frommoisture or other environmental hazards. It reduces joint stress andimproves reliability of the structure, allowing low cost substrates tobe used. Most importantly, it compensates for any thermal expansiondifference between the chip and the substrate. The underfillmechanically “locks together” chip and substrate so that differences inthermal expansion do not break or damage the electrical connection ofthe bumps.

The substrate and underfill are insulators and critical in the processof electronic packaging. A low thermal expansion coefficient (CTE) inthe underfill prevents a thermo-mechanical mismatch between the die andthe substrate. In particular, a low thermal expansion coefficient ofexpansion in the underfill prevents interference with the solderingjoint CTE (e.g. about 25 ppm/° C.). An underfill with a high CTE (e.g.70-85 ppm/° C.) may cause cracking and delamination of the structureduring operation. A material with high-temperature stability andsuperior thermal conductivity helps to maintain integrity in electronicpackaging by remaining stable while dissipating heat faster.

Such rigorous demands on materials have prompted discovery anddevelopment of alternatives to epoxy-based materials. Specifically, thedevelopment of packaging materials with improved toughness and stressmanagement for improved reliability, reduced dielectric constant forminiaturization and higher process frequencies, and rapid curing forincreased production (units per hour/UPH) and reduced cost. For newmaterials to be attractive, they must be compatible with existingprocesses and equipment and must be available at low cost.

There is growing interest in thermosetting polyimide materials for usein packaging applications. However, there remains a need to reduce theCTE of the thermoset polyimide resin to match the low CTE of the silicondie to be used as an underfill. One method to reduce CTE is addition offiller materials, but filler particles lead to higher viscosity,decreased strain to failure and have the potential for excursions due tolarge filler particles and filler settling.

Another known shortcoming of polyimide materials is the incompatiblethermoplastic and thermosetting properties with existing processes andequipment. Thermoplastic polyimides require injection molding/curing athigh temperatures and pressures, typically above 400° C. Currentpolyimide cross-linking technology is based on thermally inducedreaction of unsaturated groups such as ethynyl and phenyl leading to acomplex crosslinked product. For example, although nadimide resins,developed by NASA and others for aerospace and electronics applications,have good mechanical properties, the curing onset temperature is atleast 200° C., making it out of range of the current processes used inthe manufacturing of most microelectronic devices. Thus, there is atechnology gap that prevents widespread use of cross-linking polyimidesin microelectronics applications, namely processability and high curingtemperatures.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments are described by way of examples with reference to theaccompanying drawings, wherein:

FIG. 1A is a cross-sectional side view illustrating a base component andtwo layers of moldable material that are placed on the based component;

FIG. 1B is a view similar to FIG. 1A, further illustrating two dieshaving profiles for imprinting into the material;

FIG. 1C is a view similar to FIG. 1B, after imprinting of the materialwith the dies;

FIG. 1D is a view similar to FIG. 1C, after the material is hardenedwhile still in contact with the dies;

FIG. 1E is a view similar to FIG. 1D, after the dies are removed;

FIG. 1F is a view similar to FIG. 1E, after a thin metal layer is formedon the hardened material;

FIG. 1G is a view similar to FIG. 1F, after a thick metal layer isplated on the thin metal layer; and

FIG. 1H is a view similar to FIG. 1G, after the thick metal layer isplanarized.

FIG. 2 illustrates a cross-sectional view of a semi-conductor package;

FIG. 3A illustrates a generic structure of a dendrimer;

FIG. 3B illustrates a strained cyclic olefin used to decorate thesurface of a dendrimer;

FIG. 3C illustrates a base dendrimer or hyperbranched polymer with thecore and repeat units;

FIGS. 4A and 4B illustrate two different examples of a bisnadimidemonomer undergoing ROMP using RCC producing a thermoset polymer;

FIG. 4C illustrates a bisnorbornene monomer undergoing ROMP using RCCproducing a thermoset polymer;

FIG. 4D to 4F illustrates a low molecular weight norbornene-containingresin undergoing reactions to form a norbornene-functionalizedpolyphenylene dendrimer; FIG. 4D illustrates a low molecular weightnorbornene-containing resin undergoing condensation reaction to producean intermediate product; FIG. 4E illustrates an intermediate productnadimide-terminated imide oligomer entering ROMP using RCC to producethe final product thermoset polymer; and FIG. 4F illustrates the finalproduct, a norbornene-functionalized polyphenylene dendrimer;

FIG. 5A illustrates a generic linear polymer;

FIG. 5B illustrates a generic dendrimer/oligomer;

FIG. 5C illustrates an example of a phosphine oxide based hyperbranchedsystem.

FIG. 5D illustrates a new composition of matter where a bisphenolmonomer undergoes reaction using heat and base to produce ahyperbranched polymer.

FIG. 5E illustrates an example of a cross-linkable polyether system;

FIG. 5F illustrates an example of a hyperbranched low crystallinepolymer polyether and poly(ester); and

FIG. 5G shows an example of a hyperbranched polyquinoxaline.

DETAILED DESCRIPTION

The current state of the art for packaging materials is epoxyformulations comprising silica fillers for reduced thermal expansioncoefficient (CTE). A wide variety of resins, cross-linkers, andcatalysts are used, depending upon the processes used. For example,liquid epoxy resins are used for underfills while die attach pastes andsolid epoxy resins are used for mold compounds and substratedielectrics. Die attach films currently comprise both liquid epoxyresins for curing and thermoplastic polyimides for film formation andimproved properties. However, high temperatures required for processingprevents polyimides from being used extensively.

Imprinting process is a foundation for the move from microelectronic tonanoelectronic age. Imprinting process is not only capable of imprinting<10 micron lines traces, it has the potential of improving substrateswithout impacting costs. In essence, imprinting process provides anattractive alternative in obtaining a fast, reliable and cost-effectivesubstrates with finer feature sizes. Imprinting pattern for printedwiring board (PWB) microvias and sequential build-up provides anadvantage to traditional photoimage lithography. Imprint patterningrequires no photosensitive materials in production. The pattern isproduced directly into the face of the permanent substrate, as oppose todeveloping a temporary resist in photolithography. Imprint processingalso skips a number of traditional processes as required in thephotolithography.

The underpinning of imprinting is pressure-forming, as employed inmolding and lamination. First, an imprinter mask is made with thedesired features raised from the metal surface. Next, the imprinter iscoated with a thin layer of mold release compound to protect it andprevent sticking during the imprinting process. The substrate to bepatterned is then coated with a film of polymer. The polymer is heatedabove its glass transition temperature (Tg) where it becomesviscoelastic. The imprinter is then pressed into the polymer and thesystem is cooled back down below the polymer's Tg, thereby freezing thepattern into the polymer. The collective layers of polymers form thedielectric substrate layers. The mask is then removed and the trenchesare cleaned with either O₂ plasma or with solvents to remove anyresidual polymer that may remain in the trenches. The imprinter isreusable, thus providing cost effective lithography.

FIGS. 1A to 1H illustrate one of multiple cycles in the manufacture ofan electronics substrate of the kind to which a microelectronic die canbe mounted. A material on the substrate is imprinted (FIG. 1C), and thematerial is then at least partially cured (FIG. 1D) while still incontact with a die, so that the shape and profile of the material can bemaintained. The thermoset polyimide material disclosed in thisspecification can be used as the material to form the substrate.

FIG. 1A illustrates a base component 10 and layers of soft, moldablematerial 12. The base component 10 has a plurality of trenches 14 formedtherein. The material 12 is located on upper and lower surfaces of thebase component 10 and over the trenches 14.

FIG. 1B illustrates the components of FIG. 1A after the material 12 isplaced on the base component 10, and further illustrates imprinting dies16. Each die 16 has a profile with a plurality of raised and recessedformations 18 and 40, respectively.

As illustrated in FIG. 1C, the dies 16 are moved into contact with thematerial 12, and a force is applied that imprints the profile of thedies 16 into the material 12. Outer surfaces of the material 12 thenacquire a shape that corresponds to the profile of the respective die16. The trenches 14 allow for raised formations 18 of the die 16 topenetrate almost entirely through the material 12. The material 12 is,at this stage, suitably soft to allow for imprinting of a shape therein.

As illustrated in FIG. 1D, the material 12 is subsequently modifiedwhile being held in the profile of the respective die 16. By modifyingthe material 12, at least partial curing of the material 12 isaccomplished due to a change in composition of the material 12 from afirst composition to a second composition. Numerous mechanisms can beemployed to harden the material 12, as will be discussed herein.

As illustrated in FIG. 1E, the dies 16 are subsequently removed from thehardened material 12. FIG. 1F illustrates the structure of FIG. 1E,after a thin metal layer 22 is sputtered or otherwise deposited over thehardened material 12. As illustrated in FIG. 1G, a thick metal layer 24is subsequently plated or otherwise deposited on the thin metal layer22. As further illustrated in FIG. 1H, the thick metal layer 24 issubsequently planarized to leave metal conductors 26, only withintrenches defined in the hardened material 12.

The process of FIGS. 1A to 1H may then be repeated, with the structureof FIG. 1H acting as the base component. When the same material is usedin a subsequent cycle relative to the previous cycle, the curingtemperature profile would be the same in both layers, whereas, when adifferent material relative to the previous cycle is used in asubsequent cycle, there will be a different curing temperature profilein the different layers.

FIG. 2 illustrates a cross-sectional view of a semi-conductor package200 which uses an embodiment of the invention. The semi-conductorpackage 200 includes a substrate 201, having a semiconductor device 104mounted on a top surface of the substrate 201. The semiconductor deviceis a microelectronic die having an integrated circuit formed therein. Inone embodiment, the substrate 201 is a printed circuit board. In anotherembodiment, the substrate 201 may be a different material such assilicon or ceramic. The semiconductor device 204 is mechanically andelectrically coupled to the top surface of the substrate 201 via aplurality of solder bump connections 203. In some embodiments, the gapmay be filled with an underfill material 202 using any of the thermosetpolyimide materials as disclosed in this specification. The substrate201 contains at least one wiring layer (not shown) that electricallyconnects the device to pins or balls located along the bottom surface ofthe substrate. The solder balls 203 are placed in an array and arecommonly referred to as a ball grid array. Since the semiconductordevice 204 is flipped into place so that the solder balls 202 iselectrically and mechanically connected to the pads or lands in thesubstrate 201, the semiconductor device 204 is sometimes called a flipchip. A compliant heat transfer medium 205 known as a thermal interfacematerial. This nanocomposite phase change material fills small voids inthe major surface of the backside of the semiconductor device and thecorresponding surface of the heat spreader 106 to which thesemiconductor device 204 is attached. A heat sink 207 is attached to theheat spreader 206. The heat sink further includes a plurality of fins209 extending from the second thermal plate 208.

Combining Dendrimers or Hyperbranched Polymers to Thermoset Polyimides

The use of dendrimers or hyperbranched polymers to reduce CTE ofpackaging materials has many advantages over the use of silica fillers.Dendrimers can make a homogeneous mixture with the bulk resin, providinglittle viscosity increase compared to the large increase in viscositywith the use of particulate fillers like silica. Dendrimers andhyperbranched particles also phase separate after curing and provide amicrostructure similar to that of traditional filled system without theissue of filler settling. Also, dendrimers and hyperbranched polymers donot suffer from alpha particle emission and wire short which areproblems with silica fillers. Collectively, these advantages contributeto the properties desirable for combining dendrimers or hyperbranchedpolymers with thermosetting polyimides as a dielectric substrate layeror an underfill.

The molecular shape of dendrimers and hyperbranched polymers varies fromspherical to globular to extended geometries. The higher moleculardensity of dendrimers and hyperbranched polymers is due to the smallhydrodynamic volume of dendrimers and hyperbranched polymers compared tolinear polymers. This densely packed material is expected to have alower CTE than linear polymer due to the thermal expansion of chemicalbonds being restricted spatially by the unique molecular architecture ofdendrimers.

FIGS. 3A to 3C describe the structures of novel dendrimers orhyperbranched polymers which are used to combine with novelthermosetting polyimide to give low-CTE cured material without the useof filler. By way of illustration, these are merely examples of one ofmany dendrimers and hyperbranched polymers that can act as a componentin formulations with thermosetting polyimides for packagingapplications. The cured product will result in a lower CTE rather thanas the sole material alone.

FIG. 3A illustrates a generic structure of a dendrimer. The dendrimergenerally comprise of a core 301 which is connected to multiple repeatunits 303 and the peripheral repeat units are connected to surfacegroups 305. An example of such surface group is illustrated in FIG. 3B.FIG. 3B illustrates an example of a strained cyclic olefin used todecorate the surface of a dendrimer. FIG. 3C shows a base dendrimer orhyperbranched polymer with the core and repeat units of FIGS. 3A and 3B.This base dendrimer or hyperbranched polymer can assume a wide varietyof chemical structures. The most useful base structures are those thatgive a low CTE, such as polyphenylenes and other highly aromaticstructures including aromatic polyamides and polyesters.

Formulations employing the dendrimers and hyperbranched polymers in usewith thermosetting polyimides would be cross-linked by ring openingmetathesis polymerization (ROMP), a transition-metal catalyzed process.Upon curing, the dendrimers and hyperbranched polymers will phaseseparate from the bulk material. The formation of covalent bonds betweenthe dendrimer or hyperbranched polymer phase provides a strong interfaceand prevents phase separation until after curing, this eliminates theproblem of filler settling often seen with silica fillers.

To make a useful formulation, these dendrimers or hyperbranched polymersmay be mixed with any resin that cross-links by olefin metathesispolymerization as the bulk matrix. Examples include dicyclopentadiene,norborene, and nadimide endcapped resins. Furthermore, by way ofillustration and not by limitation, the dendrimer or hyperbranchedpolymer can at least be one of many different preparations. Forinstance, a preparation of hyperbranched polyphenylene (with norborenesurface groups) with methyol endgroups; this hyperbranched polyol canthen be esterified with 5-carboxynorbornene under standard conditions.Another example is preparation of hyperbranched aromatic polyamide withnorbornene amine surface groups. Further example is the preparation of amold compound where the hyperbranched polyphenylene with norbornenesurface sgroups (1 part), nadimide-terminated imide oligomer (1 part),and an appropriate catalyst (50 ppm) are mixed together with an overheadstirrer and passed several times through a two roll mill. The resultingmixture is then transferred to a part by resin transfer molding orsimilar technique and cured at elevated temperature.

In application, the mixture of dendrimer or hyperbranched polymer andmatrix resin is mixed with an olefin metathesis catalyst, fillers,filler modifiers, stress modifiers, flame retardant agents, mold releaseagents, or other additives to form a processable mixture. This mixturemay then be applied to parts by jet dispensing, screen printing, resintransfer molding, reaction injection molding, application of a film, orcasting. The material would be cured by heating the part to a giventemperature for a given time. Typically, these materials will be rapidlycured (in matter of minutes) at low temperatures of less than 150° C.

Using Ruthenium Carbene Complexes to Catalyze ROMP Cross-linkingReactions

The next embodiment involves using ruthenium carbene complexes (RCC) asa catalyst for polyimides to undergo ring opening metathesispolymerization (ROMP) cross-linking reaction. ROMP of polyimides usingRCC provides liquid and solid polyimide resins that can be processed andcured using current equipment and processes. The cured materials areexpected to have significantly improved properties that enable improvedreliability and higher frequencies.

The polyimides undergoing reaction are accessible synthetically. By wayof illustration and not by limitation, one example is the use of linearpolyimides. Linear polyimides used in the reaction could be prepared bycondensation of diamines with anhydrides. The cross-linking reaction,ROMP, for example, operates on nadimide compounds where simplemononadimide compounds produces polymers. This shows that it willpolymerize bis-nadimide compounds leading to cross-linked polymericstructures.

The synthesis of RCC is known in the literature. RCC is the mostappropriate catalyst system for use in current processes formicroelectronics fabrication because it possesses greater stability tothe temperature, the moisture, and the atmospheric oxygen that theproduct materials are exposed to prior to cure compared to ill-definedor early transition metal catalysts. Furthermore, recent advances in RCCprovide sufficient stability, particular ones that are temperaturelabile. Temperature labile RCCs will initiate polymerization at elevatedtemperatures of about 80° C. to about 160° C., but not at ambientstorage or use conditions. This aspect of RCC enables the use of thiscross-linking reaction for nadimide-based polyimides.

ROMP reactions of polyimides using RCC produces cross-linked polyimides.Cross-linked polyimides are high-performance polymeric materials used inmicroelectronics, aerospace and other applications. Cross-linkingprovides materials of better resilience compared to linear polymersbecause of the extensive covalent connections between polymer chains.For example, composite materials of carbon fiber and cross-linkingpolyimide matrix resins have been used to fabricate parts for spacevehicles and airplanes. ROMP has been used commercially for reactioninjection molding of cyclic-olefin monomers to producepoly-dicyclopentadiene based cross-linked materials that are tough anddurable. Furthermore, these materials have been known to make body armorand other sports equipment; they have even been evaluated forelectronics (e.g., a 131 mm thick sample of poly-dicyclopentadient has adielectric constant of only 2.49 at 1 MHz and a dielectric strength of400V/mil. Source: Materia., Inc.). Therefore, based on knowncharacteristics of ROMP products, the combination of ROMP and polyimidematerials will provide a new class of cross-linkable polyimides that areuseful in electronics packaging applications for forming dielectricsubstrates layers or underfills in substrate imprinting processes.

FIGS. 4A to 4F illustrate various examples of monomers that are used tocombine with ROMP to produce cross-linkable polyimides in electronicspackaging applications. In a group of examples, monomers are comprisedof two or more norbornene rings connected with rigid aromatic moietiessuch as phenyl, aromatic esters, amides, imides, ethers and polycyclicaromatic hydrocarbons. In another example, low molecular weightnorbornene-containing resins are prepared by condensation of adifunctional norbornene and a difunctional aromatic component withappropriate endcappers to form a low molecular weight resin withmultiple polymerizable units.

FIGS. 4A to 4C illustrate examples of polymerization of nadimidemonomers to form cross-linked polyimides. Specifically, FIGS. 4A to 4Cshow three examples of cross-linked polyimides formed from the variousbis-norbornene monomers using RCC. ROMP polymerization of variousbis-norbornene monomers to give cross-linked polyimides. In particularFIGS. 4A and 4B show two different examples of bisnadimide monomerundergoing ROMP using RCC producing a thermoset polymer. FIG. 4C shows abis-norbornene monomer undergoing ROMP using RCC producing a thermosetpolymer.

FIGS. 4D to 4F illustrates the sequence of reactions in the synthesis ofa ROMP cross-linkable nadimide-containing imide oligomers. In particularFIG. 4D shows the low molecular weight norbornene-containing resinundergoing condensation reaction to produce an intermediate product inFIG. 4E. FIG. 4E shows the intermediate product entering ROMP using RCC.FIG. 4F shows the final product, an example of the cross-linkednadimide-containing imide oligomer.

Three specific examples will now be described. First is an example ofthe polymerization of monomers to form cross-linked polymers,specifically, the preparation of4-[3-(3,5-dioxo-4-azatricyclo[5.2.1.0^(2,6)]dec-8-en-4-yl)phenyl]-4-azatricyclo[5.2.1,0^(2,6)]dec-8-ene-3,5-dione.1,3-diaminobenzene and two equivalents of4-azatricyclo[5.2.1.0^(2,6)]dec-8-ene-3,5-dione (nadimide) are combinedwith toluene (20 wt % solids) in a three-neck round-bottom flaskequipped with a Dean-Stark trap and condenser. The mixture is stirredwith heating to reflux. Water is removed from the reaction as theazeotrope reacts with toluene and condenses in the Dean Stark trap.Solvent is removed to afford the product, which may be purified byrecrystallization.

A second example is the preparation of imide oligomer with norbornenylunits at chain ends and in main chain. Nadimide, p-diaminobenzene, andpyromelletic dianhydride are combined in a 2:2:3 molar ratio indimethylacetamide (DMAC) and stirred for several hours at 120° C.Toluene is then added and the mixture is refluxed for azeotropic removalof water. The remaining toluene is then removed by distillation and themixture is precipitated into a blender containing an excess of deionizedwater and then dried in vacuo.

A third example is the preparation of a molding compound. The imideoliogomer (1 pt), dicyclopentadiene (1 pt), silica filler (2 pt),norbornen-5-yltriethoxysilane (0.01 pt), and an appropriate catalyst(100 ppm) are mixed together and passed through a two roll mill. Theresulting mixture is then transferred to a part by resin transfermolding or similar technique and cured at elevated temperature.

The thermal and mechanical properties including CTE of the cross-linkedpolyimide can be controlled by altering the molecular weight of theresins. For example, by way of illustration and not limitation, theamounts of components such as endcapper, diamine, and dianhydride asused in the polyimide oligomer illustrated in FIGS. 4D to 4F, can bealtered to customize the molecular weight of the product. Lowermolecular weight oligomers have lower viscosities during processing andhigher final cross-link densities, while higher molecular weightoligomers have higher viscosities during processing but the final curedproduce would be very tough with high flexural and tensile strengths andK_(1C). Furthermore, chemical structure of the oligomers can be tailoredby altering the structure of the components, which would modulate thethermal and mechanical properties and the dielectric constant of thecross-linked polymer. Structural flexibility also gives the possibilityof creating oligomers with crystal phases. For instance, as oppose towhat's shown in FIGS. 4D to 4F where norbornene units are illustrated asendgroups, norbornene units could also be incorporated as pendantgroups.

In typical applications, mixtures of monomers and resins, solvents,stress modifiers, filler modifiers, filler and various other componentswould be combined to provide processable materials that give the desiredproperties in the final cured product. Specifically, the resinsdescribed above are likely to be solids at room temperature and could bemixed with either a solvent or a reactive diluent such asdicyclopentadiene or some derivative thereof to give a mixture that hasproperties amendable to the process used to apply the material. If mixedwith a reactive diluent, the properties of the cured material would bemodified. In particular, lower CTE is expected from the highercross-link density provided by incorporation of dicyclopentadiene orrelated monomers. Cyclic olefin molecules appended with atrialkoxysilane moiety could be added and would incorporate the fillerinto the cross-linked polymer via covalent chemical bonds. This isanalogous to the epoxide-containing trialkoxysilanes used in the currentepoxy technology to improve the performance of filler by altering thefiller-bulk polymer interface. Flame resistance or retardance could beprovided by halogenated or phosphate ester containing diamines ordianhydrides. This is yet another added benefit particularly appropriatefor materials used to form substrate dielectric and underfill which canexperience high heat.

A critical component of this embodiment is the use of a latent catalystfor which the initiation of cure can be controlled by temperature.Controlling the cure temperature is important when formulating materialsamenable to application by jet dispensing, screen printing, casting, orlaminating. Some examples of such latent catalysts are N-heterocycliccarbene complexes of ruthenium known in the art. These catalysts arestable to air and moisture and will not initiate polymerization or cureuntil a certain temperature is reached. The temperature of initiation isin turn modulated by the structure of the carbene ligand and otherligands. For instance a more sterically bulky carbene ligand willincrease the temperature of polymerization initiation while a morelabile phosphine ligand will decrease the temperature of polymerizationinitiation. The general category of cross-linkable polyimide materialsdescribed in this embodiment can also be preformed by resin transfermolding or reaction injection molding, which are currently used fordicyclopentadiene (DCPD) and polyimides in other contexts.

Using Hyperbranched / dendritic Materials in Imprinting Process

The use of dendritic / hyperbranched materials can be used to solveseveral problems associated with nanoimprint lithography. Currentnanoimprint lithography production is limited to performing one level ofprocessing while maintaining the same resolution demonstrated in thepolymer imprinting layer so fine metal line structures can be formed andalso connected to the next layer via use of via's. The second and upperlayer often has to be processed with great care so that the processingtemperature or the material flow properties do not erase or deform theimprinted layer below. Dendritic / hyperbranched materials can bemodified to have different Tg, for instance a high Tg for the bottomlayer and a low Tg for the top layer, therefore processing temperaturesof the different layers can be different (where top is about 50° C.lower than bottom) so that forming an upper layer will not deform thebottom imprinted layer.

Second, nonvertical walls lead to tearing and detachment of the metalfilm during liftoff of the mask. This can occur in imprint lithographyif the imprinting element does not have vertical sidewalls or if thenonvertical sidewalls in the substrate result from descumming inremoving residual polymer from the bottom of the imprinted feature.Dendritic / hyperbranched materials can be formed with a high Tg thathas low viscosity in the melt during impriting process yet undergo highcross-link density during curing without loss of mechanical propertiessuch that the material cures rapidly to maintain good featureregistration during impriting and finally undergoes little shrinkageduring processing. Furthermore, Dendritic / hyperbranched materials canbe formed to have low dielectric constant and loss, good thermalstability, a low CTE (<50 ppm) below Tg and good adhesion to varioussubstrates metal (especially copper (Cu)).

Dendritic / hyperbranched materials are synthesized by thepolymerization of A2B and AB2 monomers. High molecular weight polymersystems that are highly branched can be synthesized and the polymer canbe selectively synthesized with high functionality at chain ends.Presence of high molecular weight provides mechanical robustness tomaintain features of the imprint. Further, polymers that are highlybranched have low viscosity at high temperature, making them excellentcandidates for imprinting. The hyperbranched materials when formulatedwith reactive diluents such as epoxy, cyanate esters etc. can be curedduring and after the imprinting process. When cured, these structuresform a hybrid material. The hybrid material has many advantages andbenefits in electronic packaging applications for use as a dielectricsubstrate layer or an underfill. For example, the spherical nature ofthe hybrid material contributes to a low viscosity (as compared tolinear or cross-linked materials) during processing, low shrinkage, andhigh functionality for adhesion. The hybrid material has a lowvolatility from the hardeners, resulting in lower voids, and lowerstress in the films because of low shrinkage. The hybrid materials arealso expected to have very high Tg (greater than 125° C.) and highthermal stability, thus being compatible to 460° C.

FIGS. 5A to 5B illustrate the differences between linear polymers anddendrimer/oligomers. FIG. 5A illustrates a linear polymer. The linearpolymer is polymerized from monomers 501. The linear polymer 502 has twoend groups and repeat units in the middle. Linear polymers are generallydefined by the number of repeat units (n). The number of repeat units(n) defines the molecular weight of the polymer. While the number ofrepeat units (n) also controls the mechanical properties, the solubilityand the polarity, the reactivity (especially cross-linking) iscontrolled by the end groups.

FIG. 5B illustrates a dendrimer/oligomer. The dendrimer/oligomer ispolymerized from an AB2 monomer. The dendrimer has multiple repeat unitsand multiple branch points in the middle while having multiple endgroups. Compared to linear polymers and oligomers, dendrimers areapproximately spherical in shape and have large number of end groups andare densely packed as illustrated in FIGS. 5A and 5B. Dendrimers'spherical structure contributes to a lower Rg (Radius of gyration)compared to linear polymer. Thus, for a same number of repeat units (n)as the linear polymer, the Dendritic / hyperbranched material has alower viscosity compared to the linear form of the polymer. Also, in adendrimer, there is less entanglement for the same number of repeatunits (n) so the dendrimer results in less shrinkage, thus leading tohigher Tg materials. End groups of dendrimers are in close proximity,allowing faster reactions, cross-linking or adhesion, and alsocontributes to the solubility properties of the polymer.

Hyperbranched materials are in the same class, but a variation ofdendrimers. Hyperbranched materials tend to be less regular and moreamendable for industrial scale up. The advantages ofdendrimers/hyperbranched materials over linear polymers for electronicpackaging applications can be described in the summary table below:

(Comparison to) Hyperbranched Properties During Properties Post Linearpolymers or Material Features Processing Processing thermoset SphericalShape Low viscosity Low shrinkage High viscosity for linear Lowviscosity but high shrinkage for thermosets High functionality Highreactivity of Higher hardness Linear - has only functional groups(scratch resistance) functionality at two Faster cure Higher functionalends. Lead to higher Tg groups Linear - curing is materials Chemicalresistance slow. higher crosslink Linear - thermosets density have highcross-link density leading to typically poor adhesion to interfaces.High molecular Higher Tg Tg mainly controlled weight Mechanical bybackbone robustness

Now examples of dendrimers/hyperbranched materials will be described.FIGS. 5C to 5G show examples of dendrimers/hyperbranched materialssuitable for electronic packaging applications. FIGS. 5C, 5D and 5Gillustrate three examples of hyperbranched polyether systems. FIG. 5Cillustrates an example of a phosphine oxide based hyperbranched system.Aromatic fluorides react with phenols under basic condition vianucleophillic aromatic substitution to give the hyperbranched polymerproducts. The product can be used to modify polymer systems for betterperformance as described above in [0071].

FIG. 5D illustrates an example of a phosphine oxide based hyperbranchedsystem. Aromatic fluorides react with phenols under basic condition vianucleophillic aromatic substitution to produce a hyperbranched polymer.Similarly, this product can be used to to modify polymer systems forbetter performance as described above in [0071].

FIGS. 5E shows an example of polymerization of a cross-linkablepolyether system with an epoxy resin. FIG. 5E shows an epoxy formulatedhyperbranched material cross-linked on cure using hydroxy functionalgroups. Note that cross-linking is not limited to epoxy, other compoundssuch as cyanutares, acrylates, OCN etc. can be used. Thermal and photocross-linking can also be easily formulated. As shown, the phenolicfunctional groups react with the epoxy groups via phosphine catalysis toproduce the crosslinked product. This product can be used to modifypolymer systems for better performance as described above in [0071].

FIG. 5F shows an example of a hyperbranched low crystalline polymer(LCP) polyether and poly(ester). As shown, the ester groups react withthe phenol groups to produce the hyperbranched polymer. This product canbe used to modify polymer systems for better performance as describedabove in [0071].

FIG. 5G shows an example of a hyperbranched polyquinoxaline which can bemodified as polyethers for both cross-linked and uncross-linkedmaterial. As shown, illustrates an example of a phosphine oxide basedhyperbranched system. Aromatic fluorides react with phenols under basiccondition via nucleophillic aromatic substitution. The product can beused to modify polymer systems for better performance as described abovein [0071].

While certain exemplary embodiments have been described and shown in theaccompanying drawings, it is to be understood that such embodiments aremerely illustrative and not restrictive of the current invention, andthat the embodiments are not restricted to the specific constructionsand arrangements shown and described since modifications may occur tothose ordinarily skilled in the art.

1. A method of providing a microelectronic package comprising: mountingan integrated circuit chip onto a substrate, the substrate including adielectric layer; filling a space between the chip and the substratewith a non-conducting material, wherein the dielectric layer and thenon-conducting material are each selected from a group consisting of: aformulation resulting from a cross-linking reaction of dendrimers andhyperbranched polymers with a thermoset polyimide; a cross-linkablepolyimide resulting from a cross-linking reaction of a reactantpolyimide, the cross-linking reaction catalyzing by a transition metal,and a spherical, hybrid dendrimer or hyperbranched polymer with multiplerepeat units, multiple branch points, and multiple end groups.
 2. Themethod as in claim 1 wherein the cross-linking reaction is aring-opening metathesis polymerization (ROMP).
 3. The method as in claim2 wherein the transition metal catalyst is a ruthenium carbene complex.4. The method as in claim 1 wherein the reactant polyimide furthercomprises two or more norbomene rings connected with rigid aromaticmoieties such as phenyl, aromatic esters, amides, imides, ethers, andpolycyclic aromatic hydrocarbons.
 5. The method as in claim 1 whereinthe reactant polyimide is a low molecular weight norbomene-containingresin with multiple polymerizable units that is prepared by acondensation reaction of a difunctional norbomene and a difunctionalaromatic component with appropriate endcappers.
 6. The method as inclaim 5 wherein the low molecular weight norbomene-containing resin withmultiple polymerizable units are ROMP-cross-linkable nadimide-containingimide oligomers.
 7. The method as in claim 5 wherein norbornene unitsare incorporated as pendant groups.
 8. The method as in claim 1 whereinfilling a space with a non-conducting material comprises: jetdispensing, screen printing, casting, or laminating the non-conductingmaterial; and using a latent catalyst to control a cure initiation ofthe material.
 9. The method as in claim 1 wherein a base structure forthe dendrimers or the hyperbranched polymers includes polyphenylenes,aromatic polyamides and polyesters.
 10. The method as in claim 9wherein: the dendrimers or hyperbranched polymers are mixed with resinsuch as dicyclopenadiene, norbomene, and nadimide endcapped resin, thatcrosslinks by olefin metathesis polymerization as bulk matrix; and thedendrimers or hyperbranched polymers are applied by jet dispensing,screen printing, resin transfer molding, reaction injection molding,application of a film or casting.